Diepoxides of omega-alkenylbicycloheptyl compounds



United States Patent Int. Cl. 007d 1100 p v US. Cl. 260-348 4 Claims ABSTRACT OF THE DISCLOSURE Diepoxides of omega-alkenylbicycloheptyl compounds having the formula: v

. CH CH n- CH-CH wherein n is an integer of from 1 to 16 and y is an integer of from 0 to 3. They may be reacted with organic hardeners to produce curable resins. They may also be employed as plasticizers for vinyl resins.

Z wherein each R, independently, designates an alkyl radical, preferably containing from 1 to 4 carbon atoms, and each Z, when taken individually, designate hydrogen, and when taken collectively, designate the radical wherein y is an integer having a value of from 0 to 3.

It is to be noted that, as herein employed, the symbol a1 designates one-third of an atom of aluminum. Thus, in all instances, each aluminum atom is attached to three other atoms, as in tri(bicyc1o[2.2.lJhept-Z-yl)aluminum.

Suitable bicycloheptene compounds, i.e., compounds containing a bicycloheptene structure, which can be emloyed as a reactant include, by way of illustration, bicyclo[2.2.1]hept-2-ene itself, dicyclopentadiene, tricyclo- 3,455,966 Patented July 15, 1969 ice pentadiene, tetracyclopentadiene, and pentacyclopentadiene. The bicycloheptene type reactant can also be substituted on one or more ring carbon atoms by alkyl or cycloalkyl radicals as long as the two carbon atoms which together make up the double bond of the bicycloheptene ring remain unsubstituted so as to prevent steric hindrance.

The isoalkylaluminum compounds which can be reacted with the low molecular weight bicycloheptene compounds are the triisoalkylaluminums and diisoalkylaluminum hydrides represented by the formulas:

(III) a Auombrna it d t i R HAMOHA'JH);

wherein R is as defined above. Suitable isoalkylaluminums include, by way of illustration, triisobutylaluminum, tri-2- methylbutylaluminum, tri-Z-ethylhexylaluminum, diisobutylaluminum hydride, di-Z-methylbutylaluminum hydride, di-Z-ethylhexylaluminum hydride, and the like. The preferred isoalkylaluminum is triisobutylaluminum. Isoalkylaluminums containing two or three different isoalkyl radicals can also be employed as a reactant.

In producing the bicycloheptylaluminum compound, the proportion of bicycloheptene :compound to isoalkylaluminum compound can vary, but preferably, a proportion of about 3 moles of bicycloheptene compound per mole of isoalkylaluminum compound is charged. In addition, when desired, an inert organic solvent can be incorporated in the reaction mixture. Suitable solvents include, for instance, heptane, octane, decane, benzene, toluene, xylene, decalin, and the like.

The reaction temperature can vary broadly in the range of from about 70 C. to about 200 C., substantially lower temperatures engendering an excessively slow rate of reaction, while at higher temperatures, undesirable side reactions may occur. Preferably, a reaction temperature of from about C. to about C. is employed. At such temperatures, the reaction is generally carried out for a period of from about 1 to about 10 hours. However, longer or shorter reaction periods sufiicient to produce the desired polymer can also be employed.

It has also been found preferable, during the course of the reaction, to remove the isoolefin formed as a byproduct. Concordant therewith, the reaction can be carried out in an open system under atmospheric pressure, or in a closed system under autogenous pressure, pro viding the system is equipped, in the latter instance, with means for venting or removing the by-product. The removal of by-product isoolefin serves to drive the reaction to completion and minimizes or eliminates side reactions between the isoolefin and the desired product.

The bicycloheptylaluminum compound thus obtained is ordinarily liquid at room temperature, and can be recovered from the reaction mixture upon removal of the more volatile components of the reaction mixture by distillation or evaporation, etc.

The bicycloheptylaluminum compound is then subjected to a growth process by reaction with ethylene in the absence of a catalyst, and preferably under pressure. This reaction can be represented by the partial equation:

wherein Z is as defined above and n is a positive integer equal to the number of moles of ethylene per bicycloheptylaluminum unit. Thus, in the growth process, ethylene units are inserted between aluminum atoms and adjacent carbon atoms. In addition, the grown product may contain bicycloheptylaluminum units which have not reacted with ethylene.

The amount of ethylene reacted should be sufficient to effect the growth of the bicycloheptylaluminum compound to the extent desired, as determined, for instance, by the subsequent use of the grown product. Useful products, by way of illustration, are those in which the bicycloheptylaluminum units have grown by an average varying chain length of from 2, and preferably from 6, t about 32 carbon atoms, i.e., wherein n designates an integer having a value of from 1 to about 16. To this end, the bicycloheptylaluminum compound for which growth is desired is reacted with ethylene in a proportion of at lea t 1 mole, and preferably from about 3 moles, to about 16 moles of ethylene per bicycloheptylaluminum unit, e.g. at least about 3 moles, and preferably from about 9 moles, to about 48 moles of ethylene per mole of tris(bicycloheptyl)aluminum compound. In practice, however, an excess over the required amount of ethylene is generally charged. If desired, an inert organic solvent such as those previously described in connection with Equation I can also be incorporated in the reaction mixture.

The reaction temperature for the growth process can vary broadly. Particularly good results can be obtained, for instance, in the range of from about 70 C. to about 200 C., substantially lower temperatures engendering an excessively slow rate of reaction, while at higher temperatures, undesirable side reactions may occur. More preferabIy, a reaction temperature of from about 80 C. t about 120 C. is employed, particularly in connection with a batch operation. At such temperatures, the reaction is generally carried out for a period of from about to 50 hours. However, longer or shorter reaction periods consistent with the production of the grown product can also be employed. Thus, for instance, the reaction can also be carried out continuously in a tubular reactor, at a temperature preferably of from about 120 C. to about 190 C., for very short contact periods. The amount of ethylene entering the product can be controlled in part by the control of temperature, reaction period, etc., and is readily determinable by one skilled in the art in light of this disclosure. Similarly, the reaction rate is controlled in part by the pressure, with pressures of from about 500 p.s.i. to about 5,000 p.s.i. being preferred.

After the desired amount of ethylene has been incorporated in the grown bicycloheptylalkylaluminum compound, as determined, for instance, by the moles of ethylene consumed, the system is vented so as to remove any excess ethylene. The grown product thus obtained, like its bicycloheptylaluminum compound precursor, is ordinarily liquid at room temperature, and can be recovered from the reaction mixture in any convenient manner, as for instance, by the techniques described above in connection with the recovery of the precursor.

The grown bicycloheptylalkylaluminum compound can be subjected to a displacement process by subsequent reaction with ethylene, preferably in the presence of an aluminum displacement catalyst and under pressure, to

, 4. form. an omega;-alk enyl-bicycloheptyl derivative. This, reaction ,with. ethylene can be represented. by. the partial equation:

wherein Z and n are as definedabove.

In the displacement process, the grown bicycloheptylalkylaluminum compound 'is reacted with ethylene in 'a proportion of at least l-mole ofe'thylene per bicycloheptylalkylaluminum unit thereof,'e.g'., at least 3 moles of ethylene'per mole 'ofgrowri tris(bicycloheptylalkyl) aluminum compound. In practice, howeven'an excess over the required amount of ethylene is generally charged; "If desired, an inert organic solvent such as those described above in connection with Equation I can also be incorporated in thereaction mixture; In addition, thepresence of a small amount of an acetylenic compound, 'such as phenylacetylene, has been found to minimize the migration of double bonds in the'pr'oduct. 7

Suitable aluminum displacement catalysts are known'in the art. and include nickel, cobalt, and platinum. Such metals can be incorporated in the reaction mixture in elemental form, or preferably, as an inorganic or organic salt, such as nickel chloride, platinum chloride, cobalt chloride, nickel acetylacetonate, platinum acetylacetonate, cobalt acetylacetontae, and the like. The use of such salts ordinarily engenders a better dispersion of the metal in the reaction mixture. The catalyst is generally employed in a concentration of from about 0.0001 to about 1 percent by weight of metal based upon the weight of the polymer undergoing reaction, although higher or lower catalytic amounts can also be used. Preferably, the catalyst is employed in a concentration of from about 0.005 to about 0.1 percent by weight based in like manner.

The reaction temperature for the displacement process can also vary broadly, typically in the range of from about 25 C to about 350 C. Particularly good results can be obtained in connection with a catalytic reaction in range of from about 25 C. to about 200 C. Here again, substantially lower temperatures engender an excessively slow reaction rate, While at higher temperatures, intthe presence of the catalyst, undesirable side'reactions mayoccurJThepr'eferred catalytic reaction temperature is from about 40 C. to'about C. At such temperatures the reaction is generally carried out for a-period of froni about 1 to about 24 hours. However, longer or shorter reaction periods can also be employed. T he displacement process can also be conducted omitting the use of a catalyst at substantially higher reaetion'teniperatures of up to about 350 C. or slightly higher, and preferably from 250 C. to about 320 C. At such higher temperatures, the reaction is best carried out continuously in a tubular reactor for short contact periods. As in the growth process, the reaction rateis controlled in part by .the pressure, with pressures offrom about 500 p.s.i. to about 5000 p.s.i. bang Preferred.

The product thus obtained is ordinarily liquid'ateroom temperature and can be recovered from the reaction mixture by any of the conventional separation techniques described above. For instance, theproduct can be recovered as the residue obtained upon removal of the more volatile components of the reaction mixture by distillation. Alter,- natively, the reactionrriixture can be hydrolyzed to assist the removal of alk'yla'luminu'm' formed as a b'yproduct Hydrolysis can be effected by reaction with water, aqueous 15-(27-octacosenyl)heptacyclo[9.6.1.1"" 1 O v0 7]eicos-S-ene,. I ,14-( 3l dotriacontenyl)heptacyclo[9611 1 50 3 7-(3-butenyl)nonacyclo[10.9.1L1 1 1 0 0 0 0 ]pentacos-l G-ene, 6-(5-hexenyl)nona'cyclo[ 10.9.1.1 1 1 0 0 0 0 ]pentacos-1 6-ene, 7*(5-hexenyl)nonacyclo[10.9.1.1 l "1 "O 0 0 0 pentacos-lG-ene, 6-(7-octenyl)nonacyclo[10.9.1.1 1 1 O 0 0 0 ]pentacos-16-ene, 7-(7-octenyl)nonacyclo[ 10.9.1.1 1 1 "0 "O 0 0 ]pentacos-16-ene, I 6-(9-decenyl)nonacyclo[10.9.1.1 1 1 0 0 0 0 ]pe11tacos-16ene, 7-(9-decenyl)nonacyclo 10.9.1.1 1- 1 0 0 0 0 ]pentacos-16-ene, 6-(1l-dodecenyl)nonacyclo[l0.9.1. 1 1 "1 0* 0 O 0 ]pentacos-l 6-ene, 7-(11-dodecenyl)nonacyclo[10.9.1.1 1 1 0 0 '0 0 ]pentacos-16-ene, 6 l3-tetradeceny1)nonacyclo 10.9.1.1 1 1 0 0 0 0 ]pentacos-l 6-ene, 7-(13-tetradecenyl)nonacyclo [10.9.1.1 1 1 0 0 0 0 ]pentacos-16-ene, 6-(15 hexadecenyl)nonacyclo[10.9.1.1 1 l 0 0 0 0 pentacos-l 6-ene, 7-( l5-hexadecenyl)nonacyclo l0.9.1.1 1 1 0 0 0 0 ]pentacos-16-ene, 6-(17-oetadecenyl)nonacyclo[l0.9.l,1 1 1 0 0 0 0 pentacos-l 6-ene, 'Z- (17-octadecenyl)nonacyclo[l0.9.1.1 l l 0 0 0 3 0 ]pentacos 16-ene, I 6'-(21 docosenyl)nonacyclo[10.9.l.1 l l 0 O 0 0 ]pentacos 16 ene, 7-(21-docosenyl)nonacyclo[10.9.1.15 1 1 0 90 0 0 ]pentacos-16-ene, 6 (25-hexacosenyl)nonacyclo [1091. I 1 1 0 0 0 0 ]pentacos-16-ene, 7- 25 -hexacosenyl)nonacyclo 10.9. 1 1 19 1 0 0 O 0 ]pentacos-16-ene, 6-(29-triacontenyl)nonacyclo[10.9.1.1 1 1 0 0 0 0 ]pentacos-16-ene, 7-(29-triacontenyl)nonacyclo 1O.9.'1 .1 1 1 O 0. 0 0 ]pentacos-16-ene, and the like.

The omega-alkenylbicycloheptyl derivatives can subsequently be polymerized in accordance with conventional process for the polymerization of olefinically unsat u rated compounds to produceuseful polymers. These compounds can also be reacted in accordance with conventional processes for the epoxidation of olefinically unsaturated compounds to produce the vicinal mono-"and diepoxides represented by the formulas:

wherein 'riand y are as defined above.

The formation of a mono-or diepoxide will depend, in addition to the number of unsaturated groups present in the omega alkenylbicy'cloheptyl compound, for the most part, upon the amount of epoxidizing agent employed, and is readily determinable by one skilled in they art in light ofthis disclosure. It is to be noted that the reaction of the omega-alkenylbicycloheptyl compound with an amount of epo'xidi'zing agent suflicient to produce a monoepoxide will generally result in the epoxidationofthe unsaturated groupinthe ring rather than the omega-alkenyl radical. Mixtures of monoand ldiepoxides may also be produced depending, for instance, upon the amount of epoxidizing agent employed.

'The epoxidatiton of the omega-alkenylbicycloheptyl compound can be carried out by reaction with peracetic acid or other conventional epoxidizing agent, in a suitable solvent such as ethyl acetate, if desired, and at a temperature which can vary broadly in the range of from about 25 C. to about 150 C. Preferably, reaction temperatu res otfrom about 10 C. to about 90 C. are employed. At such temperatures, a reaction period of from about 1 to about 10 hours is usually sufiicient for a complete reaction. However, longer or shorter reaction periods consistent .withepoxide formation can also be employed. The epoxide product can then be recovered from the reaction mixture in any convenient manner. For instance, the epoxide product can be recovered as the residue obtained upon removal of the more volatile components of the reaction mixture by distillation or evaporation, and

resolved, if desired, by further distillation when more than one epoxide is produced. i 7 As typical of the epoxides produced in accordance .with the invention, there can be mentioned:

2-epoxyethylbicyclo[2;2.1]heptane, Y

2- (7,8-epoxyoctyl) bicyclo [2.2. l] heptane,

2, (9, l'O-epoxydecyDbicyclo [2.2. 1 heptane,

2-( 1 l, 1'2-epoxydodecyl) bicyclo [2.2.1] heptane, 2-(l'3,14-epoxytetradecyl) bicyclo [2.2. l']heptane, 2-(15,16-epoxyhexadecyl)bicyclo[2;2.l]heptane, 2-'(l7,18-'epoxyoctadecyl)bicyclo[2.2.1]heptane,

, 2- 2 l ,22-epoxydocosyl) bicyclo [2.2. 1 heptane,

9 8-(11,12-epexydodecyl)tricyclo[5.2.1.0 ]dec-3-ene, 9-(11,12-epoxydodecyl)tricyclo[5.2.1.0 ]dec-3-ene, 8-(13,14-epoxytetradecyl)tricycle[5.2.1.0 ]dec-3-ene, 9- l 3, 1 4-epoxytetradecyl tricycle [5 .2. 1.0 dec-3-ene, 8- l5 1 6-epoxyhexadecyl) tricycle [5 .2. 1 .0 dcc-3-ene, 9- 15 l 6-epexyhexadecyl) tricycle [5 .2. 1 .0 dec-3-enc, 8-(17,18-epoxyoctadecyl)tricyclo[5.2.1.0 dec-3-ene, 9- 17,1 S-epoxyoctadecyl) tricyclo[5.2.1.0 dec-3-ene, 8-( 19,20-epoxycosyl)tricyclo [5.2.1 .0 ]dec-3-ene, 9-(19,20-epoxycosyl)tricycle[5.2.1.0 ]dec-3-ene,

8- (23,24epexytetracosyl)tricycle[5.2.1.O dec-3-ene, 9- (23 ,24epoxytetracesyl)tricycle [5.2.1.0 dec-3-ene, 8 (27,28-ep oxyoctacosyl tricycle [5 .2. 1 .0 dcc-3-ene, 9-(27,28-epoxyoctacesyl)tricyclo [5.2.1 .0 dec-3-ene, 8-(3 1,32-epoXydotriacentyl) tricycle [5.2.1.0 ]dec-3-ene, 9- (3 1,32-epoxydotriaconty1) tricycle 5 .2. 1 .0 dec-3 -ene, 3,4-epoXy-8-vinyltricyclo [5.2.1 .0 ]decane,

3 ,4-epoxy-9-vinyltricyclo[5.2.1.0 decane, 3,4-epeXy-8- 3-butenyl) tricycle [5 .2. 1 .0 decane, 3,4-epoxy-9-(3-butenyl)tricycle [5.2. 1.0 decane, 3,4-epoXy-8- 5 -hexenyl) tricycle 5 .2. 1 .0 decaue,

3 ,4-epoxy-9- (S-heXenyl) tricycle [5 .2. 1 .0 decane, 3,4-epoxy-8-(7-octenyl)tricyclo[5.2.1.0 ]decane, 3,4-epoXy-9- (7-octenyl tricycle 5.2. l .0 decane, 3,4-epoxy-8- (9-decenyl tricycle [5 .2. 1 .0 decane,

3 ,4-epoxy-9- (9-decenyl tricycle [5.2.1.0 ]decane, 3,4-ep oXy-8-( l l-dodecenyl) tricycle 5.2. l .0 decane,

3 ,4-epoXy-9-(1 l-dodecenyl)tricyclo[5.2.1.0 ]decane, 3,4#epoXy-8-( l3-tetradecenyl) tricycle [5.2.1.0 decane, 3 ,4-ep oxy-9-( l3-tetradecenyl) tricycle [5 .2. 1 .0 decane, 3 ,4-epeXy-8-( IS-heXadecenyI) tricycle [5 .2. 1 .0 decane, 3 ,4-epoxy-9-( l5-hexadecenyl)tricyclo [5.2.1 .0 decane, 3,4-epoxy-8- l7-octadccenyl tricycle [5.2.1 .0 decane, 3,4-epoxy-9-( l7-ectadecenyl)tricyclo[5.2.1.0 ]decane, 3,4-epoxy-8-( 19-eicosenyl) tricycle [5 .2. 1 LU decane, 3,4-epeXy-9- 1 9-eicosenyl tricycle [5 .2. l .0 decane, 3,4-epoxy-8- (23-tetracesenyl tricycle [5 .2. l .0 decane, 3 ,4-epoXy-9- (23 -tetraceseny1)tricyclo[5.2.1.O Jdecane, 3 ,4-ep oxy-8- 27-octacosenyl) tricycle 5 .2. 1 decane, 3,4-cpexy-9- (27-octacosenyl) tricycle 5.2. l .0 decane, 3,4-epoxy-8- (3 l-detriacentenyl) tricycle .2. 1 0] dccane,

3,4-epoxy-9-(3 l-dotriacentenyDtricycle [5.2.1.0 decaue,

3,4-epoXy-S-epoxyethyltricyclo [5.2. 1.0 decane,

3 ,4-epoXy-9-epoxyethyltricycle [5 .2. 1 .O decane,

3 ,4-epoxy-8- (3 ,4-epoxybutyl tricycle 5 .2 1 ,0 decane,

3,4-epoxy-9- (3 ,4-epoxybutyl) tricycle [5 .2. 1 .0 decane,

3,4-epoxy-8-(5,6-epoxyhexyl)tricyclo[5210 ]decane,

3,4-epoxy-9- 5 ,6-epoxyhexyl) tricycle [5 .2. 1 .0 decane,

3,4-epexy-8-(7,8-epoxyoctyl) tricycle[5.2.1.0 decane,

3,4-epoxy-9-(7,8-epeXyoctyl tricycle 5 .2. 1 .0 decane,

3,4-epoxy-8- (9, 1 O-epoxydecyl) tricycle 5 .2. 1 .0 decane,

3,4-ep exy-9- (9, 1 O-epoxydccyl) tricycle [5 .2. 1 .0 decane,

3 ,4-epoxy-8- l 1, l2-epoxydodecyl) tricycle [5 .2. l .0

decane,

3,4-epoxy-9- 1 1,12-epoxydodecyl) tricycle [5 .2. 1 .0

decane,

3,4-epoxy-8-( 13,14-epoxytetradecyl) tricycle [5.2.1.0

decane,

3,4-epoxy-9-(13,14-epoxytetradecyl)tricyclo[5.2.1.0

decane,

3,4-epexy-8-( 1 6-ep oxyhexadecyl) tricycle [5 .2. 1 .0

decane,

3,4-epoxy-9-(15,16-epoxyhexadecyl)tricyclo[5.2.1.0

decane,

3,4-epoxy-8-(17,18-epoxyoctadecyl)tricycle[5.2.1.0

decanc,

3,4-epoxy-9(17,18-epoxyoctadecyl)tricycle[5.2.1.0

decane,

3 ,4-epoxy-8- 19, 10-epoxyeicosyl) tricycle [5 .2. 1 .0

decane,

3,4-epoXy-9- 19,20-ep oxyeicosyl) tricycle [5 .2. 1 .0

decane,

3,4-epoxy-8- (23,24-epoxytetracosyl) tricycle [5 .2. 1 .0

decane,

3,4-epoxy-9- (23,24-epoxytetracosyl) tricycle [5 .2. l .0

decane,

3 ,4-epoxy-8- (27 ,28-epoxyoctacosyl) tricycle 5 .2. 1 .0

decane,

3,4-epoxy-9- (27,28-epoxyoctacesyl tricycle [5 .2. 1 .0

decane,

3,4-epoxy-8-(31,32-epoxydotriacontyl)tricycle[5.2.1.0

'decane,

3,4-epoxy-9- 3 1,32-epoxydotriacontyl) tricycle [5 .2. l .0

decane,

and the like. Similar epoxides corresponding to Formulas VII, VIII, and IX above where y is an integer having a value of from 1 to 3 (i.e., derived from tricyclopcntadiene, tetracyclopentadiene, and pentacyclopcntadiene), can also be obtained.

The epoxides produced in accordance with this invention can be reacted with organic hardeners such as polycarboxylic acids or anhydrides, polyamines, or polyols to produce curable resins having a wide variety of uses, particularly as molded articles. The resins thus obtained from the epoxides of this invention, particularly the diepoxides, may be characterized by enhanced impact strength and thermal shock resistance. The diepoxides of this invention can also be employed as plasticizers for vinyl resins. The unsaturated monoepoxides of this invention, on the other hand, can be copolymerized with conventional vinyl menomers to produce resins having enhanced heat and/or light stability.

The diepoxides can also be reacted with hydrogen in accordance with conventional processes for the reduction of epexides to produce the omega-hydroxyalkylbicycloheptel derivatives represented by the formulas:

a0 y wherein n and y are as defined above.

The reduction of the diepoxide can be carried out by reaction with hydrogen under pressure in the presence of a hydrogenation catalyst such as Raney Nickel or the like, and preferably in a suitable inert solvent such as ethanol or heptanol, etc., at a temperature which can vary broadly in the range of from about C. to about 300 C. Preferably, reaction temperatures of from about C. to about 200 C. and pressures from about 400 p.s.i. to about 3,000 p.s.i. are employed. At such temperatures and pressures, a reaction period of from about 1 to about 10 hours is usually sufiicient fer a complete reaction. However, longer or shorter reaction periods can also be employed. The diol product can then be recovered and resolved, if necessary, in any convenient manner, as, for instance, by the conventional techniques described above.

As typical of the diols produced in accordance with this invention, there can be mentioned:

8- (2-hydroxyethyl) tricycle [5.2. 1 .0 decan-4-ol, 9-(2-hydroxyethyl) tricycle [5.2.1 .0 decan-4-ol,

1 l 8-(2-hydroxyethyl) tricycle [5.2.1 .0 ]decan-3-ol, 9-(2-hydroxyethyl) tricycle [5.2. 1 .0 ]dCa11-3-Ol, 8-(4-hydroxybutyl)tricyclo [5.2.1.0 ]decan-4-ol, 9- (4-hydroxybutyl) tricycle [5 .2. 1 .0 decan4-ol, 8- (4-hydroxybutyl tricycle [5 .2. 1 .0 decan-3 -el, 9'- (4-hydroxybutyl tricycle 5.2. 1 .0 decan-3-ol, 8-(6-hydroxyhexyl)tricycle[5.2.1.0 ]decan-4-ol, 9- (6-hydroxyhexyl tricycle [5.2. 1 .0 decan-4-ol, 8-(6-hydroxyhexyl)tricycle [5.2.1.0 ]decan-3-ol, 9-(6-hydroxyhexyl)tricycle[5.2.1.0 ]decan-3-ol, 8-(8-hydrexyoctyl)tricycle[5.2.1.0 ]decan-4-ol, 9- 8-hydroxyocty1) tricyclo[5.2. 1 .0 decan-4-ol, 8-(8-hydroxyectyl)tricycle-[5.2.1.0 ]decan-3-ol, 9-(S-hydroxyoctyl)tricyclo[5.2.1.0 ]decan-3-ol, 8-( 10-hydroxydecyl)tricyclo [5.2.1 .0 decan-4-ol, 9- 1 O-hydroxydecyl) tricycle [5 .2. 1 .0 decan-4-ol, 8-( 10-hydroxydecyl)tricyclo [5.2.1 .0 decan-3-el, 9-( 10-hydroxydecyl)tricyclo[5.2.1.0 decan-3-ol, 8-(12-hydroxydedecyl)tricycle[5.2.1.0 decan-4-o1, 9- 12-hydroxydodecyl) tricycle [5 .2. l .0 decan-4-ol, 8- 12-hydr0xydodecyl tricycle [5 .2. 1 .0 decan-3-ol, 9-( 12-hydroxydodecy1) tricycle [5.2.1.0 decan-3-ol, 8-( 14-hydroxytetradecyl) tricycle 5.2. 1 .0 decan-4-ol, 9-( 14-hydrexytetradecyl) tricycle 5 .2. 1 .0 decan-4-o1, 8-( 14-hydroxytetradecyl) tricycle [5 .2. 1 .0 decan-3 -01, 9-( 14-hydroxytetradecyl)tIicyclo[5.2.1.0 decan-3-ol, 8-(16-hydroxyhex-adecyl)tricyclo[5.2.1.0 ]decan-4-ol, 9-(16-hydroxyhexadecyl)tricyclo[5.2.1.0 ]decan-4-ol, 8- 1 6-hydroxyhexadecyl)tricycle [5.2. 1.0 decan-S-ol, 9-(16-hydroxyhexadecyDtricyclo[5.2.1.O ]decan-3-ol, 8-(18-hydroxyoctadecyl)tricyclo[5.2.1.O ]decan-4-0l, 9-(1S-hydroxyoctadecyl)tricycle[5.2.1.0 ]decan-4-o1, 8-(18-hydroxyoctadecyl)tricyclo[5.2.1.0 ]decau-3-ol, 9-(18-hydroxyoctadecyl)tricycle[5.2.1.0 ]decan-3-ol, 8- 20-hydroxyeicosyl tricycle [5 .2. 1.0 decan-4-el, 9- (ZO-hydroxyeicosyl) tricycle [5 .2. 1 .0 decan-4-ol, 8-(2O-hydroxyeicosyl)tricyclo[5.2.1.0 ]decan-3-el, 9-(20-hydroxyeicosyl tricycle [5 .2. 1 .0 decan-3-ol, 8- (24-hydroxytetracosyl) tricycle 5.2. 1.0 decan-4-ol, 9- (24-hydroxytetracosyl) tricycle [5.2.1 .0 ]decan-4-ol, 8- (24-hydroxytetracesyl tricycle [5.2. 1.0 decan-3-ol, 9- (24-hydroxytetracosyl tricycle [5 .2. 1.0 decan-S-ol, 8-(28-hydroxyoctacosy l)tricyclo[5.2.1.0 ]-decan-4-o1, 9- 28-hydrexyoctacosyl tricycle [5 .2. 1 .0 decan-4-ol, 8-(28-hydroxyoctacesyl)tricyclo[5.2.1.0 ]decan-3-ol, 9- (28-hydroxyoctacosyl tricycle 5 .2. 1 .0 decan-3-el, 8-(3 2-hydroxydotriacontyDtricyclo [5 .2. 1 .0 decan-4-ol, 9- 32-hydroxydotriacontyl tricycle 5 .2. 1 .0 decan-4-ol, 8-(22-hydrexydotriacontyl)tricyclo[5.2.1.O decan-3-ol, 9- 32-hydroxydotriacontyl tricycle 5 .2. 1 .0 decan-S-ol,

and the like.

The grown bicycloheptylalkylaluminum compounds obtained in accordance with Equation IV can also be converted to omega-hydroxyalkylbicycloheptyl compounds represented by the formula:

(XII) CH CH OH Z wherein Z and n are as defined above, by contacting the grown bicycloheptylalkylaluminum compound at a temperature maintained in the range of from about 0 C. to about 150 C., and preferably from about C. to about 60 C., with oxygen so as to insert an oxygen atom between each aluminum atom and the adjacent carbon atoms. Such contact can be effected, for instance, by passing dry air or a nitrogen-oxygen mixture into a reaction mixture containing the grown bicycloheptyL alkylaluminum compound. Since the reaction is exothermic, it may be desirable in certain instances to use a low concentration of oxygen at the beginning of the reaction and thereafter increase the oxygen concentration in the reactant gas stream as the rate of reaction decreases. Near the end of the reaction, pure oxygen can be used to insure completion. If desired, an inert organic solvent such as those described above in connection with the production of the bicycloheptylaluminum compound can also be incorporated in the reaction mixture.

After the oxygenation step, water or dilute acid is added to the reaction mixture to hydrolyze the oxygenated product to a hydroxyalkylbicycloheptyl compound. Water is preferred, as it readily hydrolyzes the oxygenated product, forming the hydroxyalkylbicycleheptyl compound and aluminum hydroxide as a by-product. Alternatively, the oxygenated product can be hydrolyzed by reaction with aqueous alcohol.

The hydroxyalkylbicycloheptyl compound thus obtained can be recovered from the reaction mixture in any convenient manner, as, for instance, by the conventional techniques described above. Here again, due to the nature'of the bicycloheptylalkylaluminum compound empolyed as a precursor, the product may comprise an isomeric mixture of hydroxyalkylbicycloheptyl compounds of statistically varying molecular weight (hydroxyalkyl chain length). Such mixture can also be resolved by the conventional techniques described above.

As typical of the omega-hydroxyalkylbicycloheptyl compounds produced in accordance With this invention, there can be mentioned;

2-(2-hydrexyethyl) bicyclo[2.2.1]heptane, 2-(4-hydroxybutyl)bicyclo[2.2.1]heptane, 2-(6-hydroxyhexyl)bicyclo[2.2.1]heptane, 2-(8-hydroxyoctyl)bicyclo[2.2.1]heptane, 2-( IO-hydroxydecyl)bicyclo[2.2.1]heptane, 2-( 12-hydroxydedecyl)bicycle [2.2.1]heptane, 2-(l4-hydroxytetradecyl) bicyclo[2.2.1]heptane, 2-(16-hydro'xyhexadecyl)bicyclo[2.2.1]heptane, 2-( 18-hydroxyoctadecyl) bicyclo[2.2.1]heptane, 2-(22-hydroxydocosyl)bicyclo[2.2.1]heptane, 2-(26-hydroxyhexacosyl) bicyclo[2.2.1]heptane, 2-(3 O-hydroxytriacontyDbicyclo[2.2.1]heptane, 8- (2-hydroxyethyl tricycle [5 .2. 1.0 dec-3-ene, 9-(2-hydroxyethyl)tricyclo[5.2.1.0 ]dec-3-ene, 8-(4-hydroxybutyl)tricyclo[5.2.1.0 ]dec-3-ene, 9- (4-hydroxybutyl) tricycle [5.2.1 .0 dec-3-ene, 8-(6-hydroxyhexyl) tricycle [5.2.1 .0 ]dec-3-ene, 9- 6-hydroxyhexyl) tricycle [5 .2. 1 .0 dec-3-ene, 8-(8-hydroxyoctyl)tricyclo [5.2.1.0 ]dec-3-ene, 9- S-hydroxyoctyl) tricycle 5 .2. 1 .0 dec-3-ene, 8-( IO-hydroxydecyl)tricyclo[5.2.1.0 dec-3-ene, 9-(lO-hydroxydecyl)tricyclo[5.2.1.0 ]dec-3-ene, 8-(12-hydr0xydodecyl)tricyclo[5.2.1.0 ]dec-3-ene, 9(12-hydroxydodecyl)tricycle[5.2.1.0 ]dec-3-ene, 8-( 14-hydroxytetradecyl tricycle [5.2. 1.0 ]dec-3-ene, 9-( 14-hydroxyt etradecyl) tricycle [5 .2. 1 .0 dec-3-ene, 8-( 16-hydroxyhexadecyl) tricycle [5.2.1 .0 ]dec-3-ene, 9-(16-hydroxyhexadecyDtricyclo[5.2.1.0 dec-S-ene, 8-( 1 8-hydr0xyoctadecyl) tricycle [5 .2. 1 .0 dec-3-ene, 9- 1S-hydroxyoctadecyl)tricycle[5.2.1.0 ]dec-3-ene, 8-(22-hydroxydocosyl)tricyclo[5.2. 1.0 1dec-3-ene, 9-(22-hydroxydocosyl)tricycle [5.2. 1.0 dec-3-ene, 8-(26-hydroxyhexacosyl)tricycle [5.2.1.O ]dec-3-ene, 9-(26-hydroxyhexacesyl)tricycle[5.2.1.0 ]dec-3-ene, 8- (3 O-hydroxytriacontyl) tricycle [5.2.1 .O dec-3-ene, 9-(30-hydroxytriacentyl)tricycle [5.2.1.0 dec-3-ene, 4-(2-hydroxyethyDpentacyclo[6.5.1.1 0 0 pentadec- 1 O-ene, 5 Z-hydroxyethyl) pentacyclo [6.5 1. 1 0 0 pentadec- 1 O-ene, 4-(4-hydroxybutyl)pentacyclo [6.5.1 1 0 0 pentadec-l O-ene, 5-(4-hydroxybutyl)pentacyclo [6.5.1. 1 0 0 pentadec-10-ene, 4-(6-hydroxyhexyl)pentacyclo[6.5. 1. 1 0 0 pentadec- 1 Gene, 5-(6-hydroxyhexyl)pentacyclo[6.5.1.1 0 0 pentadec-lO-ene,

15 The bicycloheptylaluminum compounds obtained in accordance with Equation I can be hydrolyzed with water, dilute acid, or aqueous alcohol to produce bicycloheptyl compounds corresponding to the bicycloheptyl units of the aluminum compound, and the grown bicycloheptyl- 16 Various side reactions which accompany the main reactions of the instant invention also give rise to a number of useful by-products. Thus, 2-isobutylbicyclo[2.2.l] heptane can be produced in accordance-with the following partial equations:

in gjqm cmcu 2 alkylaluminum compounds obtained in accordance with 25 Likewise, 2,2-binorbornane is formed by the reactions Equation IV can be similarly hydrolyzed to produce alkylbicycloheptyl compounds corresponding to the bicycloheptylalkyl units of' the aluminum compound. The hydrolysis reactions can be represented by the partial equations:

(XIII) (XIV) wherein Z and n are as defined above.

The long chain alkylbicycloheptyl compounds produced in accordance with this invention can be converted H O a1 3 l m illustrated by the partial equations:

(xvi) O K) m When dicyclopentadiene is employed instead of bicyclo[2.2.l]hept-2-ene, these side reactions result in the formation of 8(and 9)-isobutyltricyclo[5.2.1.0 ]dec-3- ene and bitricyclodencenes such as 8,8(and 9,9')-bitrito alkylbicycloheptyl sulfonates, which are of interest as 55 cyclo[5.2 1.02,s]dec 3 ene in accordance with the follow biodegradable detergents, by conventional processes.

(XVIII) alCH CH(CH a ing partial equations:

l H O (XVII In addition to the above products, tricyclo[5.2.1.0 bornane isomers in equal amounts, with the remainder de'cane is also produced as illustrated by the following partial equations:

(XIX) The invention can be illustrated further by the following examples which, however, are in no ..way intended to limit the invention.

EXAMPLE I In a SOO-milliliter flask equipped with a stirrer, thermometer, reflux condenser, jacketed dropping funnel, and attachment to a Dry Ice trap, 67 grams of bicyclo[2.2.1] hept-2-ene (0.71 mole) were added with stirring to 47 grams of triisobutylaluminum (0.24 mole) over a period of 130 minutes, at a temperature maintained in the range of from 98 C. to 100 C. Heating and stirring were then continued at the same temperature for an additional period of five hours. During the course of the'ensuing reaction, 31 grams of isobutylene" (78% of the theoretical amount) were evolved and collected in the Dry Ice trap. The reactionproduct was hydrolyzed first with ethanol, then with water, and finally with aqueous'hydrochloiic acid. During this hydrolysis, 5 grams of isobutane (12%) 4 Weight Fraction (grams) Residue The first two fractions were substantially pure bicyclo [2.2.1]heptane. The third fraction was mainly 2-isobutylbicyclo[2.2.1]heptane. with. some bicyclo[2.2.l]heptane. The fourth fraction contained 76 percent of two binorof the fraction consisting mainly of 2-isobutylbicyclo [2.2.1]heptane.

Analytically pure sample of the Z-isobutylbicyclo [2.2.1]heptane was obtained by purification with the help ofa preparative gas chromatograph (Fisher Prep/Partitioner), n =1.4534. The infrared absorption spectrum indicated the presence of a CH(CH group.

Analysis-Calculated for C H C, 86.76%; H, 13.24%; M.W., 152.3. Found: C, 87.28%; H, 13.14%; M.W., 152 (mass spectroscopy).

Recrystallization of a portion of fraction 4 from ethanol provided an analytically. pure sample of 2,2'-binorbornane.

Analysis.--Calculated for C H C, 88.35%;" H, 11.65%; M.W., 190.3. Found: C, 88.28%; H, 11.61%"; M.W., 190 (mass spectroscopy). 7

EXAMPLE 11 Four hundred and forty-six (446) grams of bicyclo [2.2.1]hept-2-ene (4.74 moles) was reacted with'3-13 grams of triisobutylaluminum 1.58 moles). in a manner similar to that described in Example Iand 562- grams of reaction product were recovered. 1

A mixture of 222 grams of this product and 424 grams of ethylene (15.1 moles) was charged to a three-liter stainless steel bomb under nitrogen. The bomb was closed and heated, accompanied by rocking, at a temperature maintained in the range of from 50 C. to .C..for a period of three hours, and then at a temperature main.- tained in the range of from 83 C.,to-87 C. for seventeen hours. The pressure in the bomb dropped during this time from 1060 p'.s.i. to 790 p.s.i. at 85, C. The bomb was vented after coolingQand the contents transferred under nitrogen to a glass flask. The bomb was then rinsed with some petroleum ether (B.P. '35-37 C.),

' which was added to the reaction product". About 90 per cent of this material was hydrolyzed with ethanol and then with dilute hydrochloric acid. The ihydrolysate formed an organiclupper layer and anaqueous lower 19 layer. The layers were separated and the aqueous layer was extracted with petroleum ether. The organic layers were then combined, dried over magnesium sulfate, filtered, and distilled through a four-foot spinning band to yield the following fractions after the removal of EXAMPLE III Four hundred and forty-six (446) grams of bicyclo- .[2'.2;1]hept-2-ene (4.74 moles) was reacted with 313 grams of triisobutylaluminum (1.58 moles) in a manner similar to that described in Example I and 562 grams of reaction product were recovered.

A mixture 239 grams of this product and 419 grams of ethylene (15 moles) was charged to a three-liter stainless steel bomb under nitrogen. The bomb was closed and heated, accompanied by rocking, at a temperature maintained in the range of from 82 C. to 87C. for a period of 17 /2 hours, whereupon the pressure within the bomb dropped from a high of 1530 p.s.i. to 1220 p.s.i. The bomb was vented at a temperature of C., and after the addition of 150 grams of petroleum ether (B.P. -37 C.), 0.15 gram of nickel acetylacetonate,

. and 220 grams of ethylene (7.9 moles), the bomb was solvent:

Weight Fraction (grams) B.P. C.) 0.. range 1 3 66-101 C5-C1 2 12 C1-C9 3 30 C7-C1] 4---- 50 185/atm.-124/50 mm. Hg (3 -0 5. 65 124/50 mm. Hg-156/50 mm. Hg- 011-015 6- 46 156/50 mm. Hg-169/20 mm. Hg 7-- 17 169/20 mm. Hg 8- 9 200/20 mm. Hg-l80/2 mm. Hg- Besidue 2 Fractions 1 through 8 were analyzed by gas chromatography. The following amounts of hydrocarbons were obtamed:

Yield, percent based on Weight bicyclo- Hydrocarbons (grams) heptene Bicyelo[2.2.1h]eptane 6. 2 3. 7 2-ethylbieyclol2.2.1]]heptane-- 28. 5 13. 2-butylblcyc1o[2.2.1 heptane..- 42. 5 16. 5 2-isobutylbicyclo[2 2 1]hep1:ane. 31. 5 12. 2 2-hexylbicyclo[2.2.llheptane 38. 1 12. 4 2,2-binorbornane 23. 3 14. 5 2-octy1bicyclo[2.2.1]heptane. 25. 9 7. 3 2-decy1bieyclo[2.2.1]]1eptane- 12. 8 3. 2 2-do ecylbicye1o[2.2 llheptane. 4. 3 1. 0 2-tetradecy1bicycloI2 2 1]heptane 2. 6+ 0 5+ 2-hexadecylb1cyclo[2 2 11heptane 0. 8+ 0. 15+ blcyelo[2.2.1]hept-2-ene 2. 0 1. 2 2-vinylbicyclo[2.2.1]heptane 2. 9 1. 4 2-(3butenyl)bicyclo[2.2.1]heptane 1. 3 -0. 5 2-(5-hexenyl)bicyclo[2.2.1]heptene 0. 7 O. 2 2-(7-octenyl)bicyclo[2.2.1]heptane 0. 4 0. 1

Corrected for the fact that only 90 percent of the reaction product was hydrolyzed.

Very small amounts of hexane, octane, decane, Z-methylheptane, and Z-methylnonane were also detected. Furthermore, about 3 percent of higher boiling materials 0 were found.

The presence of the following compounds was determined by a comparison of their retention times in corresponding fractions with those of known compounds or compounds prepared in another way:

bicyclo[2.2.1]heptane, bicycl0['2.2.1]hept-2-ene,

2-ethylbicyclo [2. 2.1 Jheptane, 2-vinylbicyclo [2.2. 1 lheptane, 2-hexylbicyclo[2.2.1]heptane,

2- (S-hexenyl) bicyclo [2.2. 1 heptane, and 2'-dodecylbicyclo[2.2.1 heptane.

lar retention times, although the retention time of theexo product was always slightly shorter.

Structures were assigned to the other compounds on the basis of their relative retention times.

resealed and heated with rocking at a temperature of from 68 C. to 71 C. for 19 hours. During this time the pressure dropped from 660 p.s.i. to 480 p.s.i. The bomb was again vented after cooling, and the contents transferred under nitrogen to a glass flask and hydrolyzed with ethanol, water, and finally with aqueous hydrochloric acid. The hydrolysate formed an organic upper layer and an aqueous lower layer. The layers were separated and the organic layer was washed with water, dried, filtered and distilled through a four-foot long spinning band to give the following fractions after removal of solvent:

B P. C C 0,, range 67-106 C5-C7 106-146.-. 07-00 146-180 09-011 180/atn1.1%/50 mm. Hg Cir-C13 128/50 111.111.-156/50 mm. Hg- 0 14315 156/50 mm./50 mm. H 0 -0 170/50 mm.200/50 mm. Hg 14-017 8-- 16 200/50 mm.l84/0.75 mm. Hg 017-023 Residue. 4

Fractions 1 through 8 were analyzed by gas chromatography. The following amounts of hydrocarbons were obtained:

Yield,

percent based on Weight bicyclo- Hydrocarbons (grams) heptene Bicyclo[2.2.1]hept-2-ene 4.8 2. 5 2-vinylbicyclo[2.2.1]heptane 38. 8 15. 8 2-(3-butenyl) bicyclo[2.2.l]heptane 33. 5 11. 1 2-isobutylbicyclo[2.2.1]hept-2-ene 26. 9 8. 9 2-(5-hexenyl)bieyclo[2.2.1]heptane 34. 0 9. 5 2-(7-octenyl)bicyclo[2 2 1]heptane 31. 9' 7. 7 2- (9-deeenyl) bicyclo[2.2.1]heptane 13. 7 2. 9 2-(11-dodecenyl) bicyclol2 2 llheptane- 4. 9 O. 9 2-(13-tetradecenyl)bicyclo[2 2 1]heptane 4. 0 0. 7 2-(l5-hexadecenyl) bicyclo[2.2.1]heptane 0. 4+ 0. 06+ 2-ethylbicyclo[2.2.1]heptane 8. 6 3. 4 2-bntylbicyclo[2.2.1]heptane 4. 3 1. 4 2-isobuty1bicyclo[2.2.1]heptane 9. 5 3. 1 2-hexylbicyclo[2.2.1]heptane 7. 5 2. 1 2,2'-binorbornane 29. 6 7. 7 2-0ctylbicyclo[2.2.1]heptane. 4. 5 1. 1 2-decylbicyclo[2.2.l]heptane 1. 5 0. 3 2-dodecylbicyclol2.2.1]heptane 0. 9 0. 17 2-tetradecy1bicyclo[2.2.1]l1eptane 0. 25 0. 04

EXAMPLE IV In a three-liter flask equipped with a stirrer, eter, reflux condenser, jacketed dropping funnel, and at:

thermomtachment to a dry ice trap, 660 grams of endo-dicyclopentadiene moles) were added with stirring to 332 grams of triisobutylaluminum (1.67 moles) over a period of nine hours, at a temperature maintained in the range of from 95 C. to 97 C. Heating and stirring were then 22 panied by rocking, at a temperature maintained in the range of from 82 C. to 87 C. for a period of twenty-one hours. The pressure in the bomb dropped during this time from 1030 p.s.i. to 675 p.s.i. The bomb was vented after cooling, and after dilution with petroleum ether (B.P.

continued at a temperature of from 96 C. to 105 C. for 5 35-39 C.), the contents of the bomb was transferred an additional period of eight hours. During the course under nitrogen to a glass flask and hydrolyzed with ethaof the ensuing reaction, 225 grams of isobutylene (80% I101, water, and finally with aqueous hydrochloric acid. of the theoretical amount) were evolved and collected in The hydrolysate formed an organic upper layer and an the dry ice trap. A 268 gram portion of the reaction pl'Odaqueous lower layer. The layers were separated and the 11d as hy yz first With ethanol, then With Water, organic layer was washed with water, dried over magand finally with aqueous hydrochloric acid. During this nesium sulfate, filtered and distilled through a four-foot hydrolysis, isobutane derived from unreacted triisobutyllong spinning band to give the following fractions after aluminum Was collected in the dry ice trap. The hydrolythe removal of solvent: sate formed an organic upper layer and an aqueous lower layer. The layers were separated and the aqueous layer Weight 0 was extracted with petroleum ether. The organic layers Fractmn (grams) 011131189 were then combined, dried over magnesium sulfate, fil- 1- 4 160-200 c o tered and distilled through a three-foot long spinning band 5 fig gggf gg -g mto give the following fractions: 4- 63 150/47 mm.150/10 mm. H 0 -0 5- 18 150 10 mm.172/5 mm. Hg 014-02 6 27 172/5 mm.187/1 mm. Hg. cut-C22 Weight 7- 7 187/1 mm.192l1 mm. Hg- 02 -0 Fraction (grams) B.P. C.) 0.. range Residue... 6

if; Po li u shi siiiiiifi ifig'll '1 8:11 F Fractioins 1 through 8 were analyzed by gas chromag iggg gjgglg g fiffi :83; tography. The following amounts of hydrocarbons were a; 145/1mm.155l0.5mm.Hg..-

Czu obtained.

NoTn.-Fraction 5 was distilled without rectification. pgtric lgi 8 Fraction 5 contained mostly petroleum ether and 7.6 ba eq grams of tricyclo[5.2.l.0 ]dec-3-ene. Fractions 1 through Weight (1536i?)- 4 were analyzed by gas chromatography. The following Hydrocarbons a s) P nt-adi n amounts of hydrocarbons were obtained: Tricycle[5.2.1.O ]dec 3-ene m 3 8(and 9)-ethyltricyelo[52.1.0 ]dec-B-ene a 40. 9 19. 6 8(and 9)-butyltricyclo[5.2.1.0 ldec-3-ene 36. 0 14. 7 Yield Pen 8(and 9)-isobuty lt icyclo[5.2.1.0 ]deo-3 ene 21.8 8.9 cent based 8(and 9)-hexy1tr1eyelo[5.2.l.0 ]dec-3-ene 23. 7 8. 4 n 283%33itttdtit at ttttiitttiitt t9 Hydrocarbons pentadlene Bitrggcloqeceng 1 6 3, Etitttlifilgfiiilfi?tffff;3j 2;; t; 38h9i tdfdtiliattArtisans-s: dz; .5;

3.4 1.5 t t i d i rattan".tsszasgasasrtaaP e Bltmyclodecene b The two isomers were detected 11]. the approximate ratio or 1;2 i th N0TEcnSisted of several isomers o is i iv gi l i i sv ho peaks were overlapping. The presence of tricyclo[5.2.1.0 ]dec-3-ene, tricyClO- About 57 percent of C C and C hydrocarbons [5.2.1.0 ]decane, and dicyclopentadiene was determined were found in fractions 6 and 7. by a comparison of their retention times in corresponding An analytically pure sample of 8(and 9)-ethyltricyclo fractions with those of known compounds or compounds [5.2.1.0 ]dec-3-ene was obtained by preparative gas prepared in another way. The compounds used for comchromatography on Fisher Prep/Partitioner, 71 parison were prepared as follows: reduction of d cyclo- 1.4 961, (i 0.941. Its infrared spectrum confirmed the pentadiene over platinum Oxide yielded tricycloassigned structure. [5.2.1.0 ]decane, hydrogenation over palladium on cal- Analysis.-Calculated for C H C, 88 32%; H cium carbonate afforded tricyclo[5.2.1.O ]dec-3-ene. 11.18%; M.W. and hydrogen number, 162.3; M 50.57. The isobutyltricyclo[5.2.1.0 ]dec-3 -enes were 1s Found: C, 89.08%; H, 10.77%; hydrogen number, 156; lated as a mixture of two isomers from a corresponding M.W., 162 (mass spectroscopy); M 50.4. fraction in Example V by preparative gas chromatography An analytically pure sample of 8 (and 9)-butyltricyclo on a Fisher Prep/Partitioner. The infrared absorption [5.2.1.0 ]dec-3-ene was also obtained by preparative spectrum indicated the precence of CH(CH groups, gas chromatography in the above manner. Inspection of d i RCHICHR' groups. its infrared spectrum did not indicate the presence of Analysis.Calculated for C H C, 88.35%; H, CI-I(CH groups as in the case of 8 (and 9)-isobutyl 11.65%; M.W. and hydrogen number, 190.3. Found: tricyclo[5.2.l.0 ]dec-3-ene (see Example IV). 88.63%; H, 11.50%; hydrogen number, 191.3; M.W., 190 Analysis.-Calculated for C I-I M.W. and hydrogen (mass spectroscopy). number, 190.3. Found: M.W., 190 (mass spectroscopy);

An analytically pure sample of the bitricyclodecelrlies hydrogennumber,186 1 was obtained b recrystallization from butanol. The w ite purified sample (3 g.) melted at 165-167 The infrared 55 EXAMPLE VI spectrum was in agreement with'the assigned structure. A mixture of 174 grams f the reaction product Analysis-"Calculated for zo z l C, 90-16%; H tained as described in Example IV and 276 grams of 9.84%; M.W., 266. Found: C, 90.24%; H, 9.75%; M-W" ethylene (9.85 moles) was charged to a stainless steel 262:2 percent (boiling point method). bomb under nitrogen. The bomb was closed and heated, accompanied by rocking, at a temperature maintained p V in the range of from 82 C. to 85 C. for a period of A mixture of 200 grams of the reaction product obsixteen and one-half hours. The pressure in the bomb tained as described in Example 1V and 260 grams of ethyldropped during this time from 1140 p.s.i. to 980 p.s.i. ene (9.3 moles) was charged to a stainless steel bomb The bomb was vented after cooling, and after the addi- Hnder nitrogen The bomb was closed and ed, acc tion of 200 grams of benzene, 0.1 gram of nickel acetyl- 23 acetonate, and 265 grams of ethylene (9.5 moles), the bomb was resealed and heated with rocking at atemperature of about 70 C. for 24 hours., During this time the pressure dropped from 810 p.s.i. to 710 p.s.i. The bomb was again vented after cooling, adn the contents transferred under nitrogen to a glass flask and hydrolyzed with ethanol, water, and finally with aqueous hydrochloric acid. The hydrolysate formed an organic upper layer and an aqueous lower layer. The layers were separated and the organic layer was washed with water, dried, filtered and distilled through a four-foot long spinning band to give the following fractions after removal of solvent, in addition to small amounts of other low-boiling materials? Weight Fraction (grams) B.P. C.) 0,. range 13 94/50 mm. Hg-110/50 mm. Hg -012 58 110/50 mm. Hg-150/50 mm. Hg- Gin-C14 150/50 mm. Hg-175/50 mm. Hg 0 2-0 19 140/10 mm. Hg-168l10 mm. Hg. Cir-Cm A mixture comprised predominantly of 8 (and 9)- vinyltricyclo[5.2.1.0 ]dec3-ene was isolated by fractional distillation (B.P. 85 C./ 10 mm. Hg-57" C./ 1.7 mm. Hg). To 795 grams of this mixture, 2658 grams of a 25.2 percent solution "of peracetic acid irfethyl "acrylate were addeddropwise with stirring over a period of four hours and five minutes at a temperature of 50 C. Stirring was then continued at a temperature of 50 C. for an additional period of five hours. and ten minutes until 99.4 percent of the theoretical amount of peracetic acid had been jconsumed. Low boiling material present was thereafter removed by codistillation with 2560 grams of ethylbenzene. The residue was then combined with the residue from a similar run of the same size which had been carried to 98.2 percent completion with peracetic acid and co-distilled with ethylbenzene. The combined residues were then distilled through a 30-inch long column to give 619 grams of a colorless liquid boiling at a temperature of 84 C./1.8 mm. Hg-89 C./1.6 mm. Hg n 1.4947), which consisted of substantially pure 3,4- epoxy-8 (and 9) ethyltricyclo[5.2.1.0 ]-decane (indicated purity of 99.5 percent by hydrogen bromide-dioxane epoxide analysis). After distillation of 131 grams of mid cuts, 1008 grams of a colorless liquid boiling at a temperature of 116 C./ 1.25 mm. Hg-126 C./ 1.5 mm. Hg (7: 1.5142) was obtained which consisted of substantially pure 3,4-epoxy-8 (and 9)-epoxyethyltricyclo[5.2.1.0 decane (indicated purity of 97.8 percent by hydrogen bromide-dioxane epoxide analysis).

7 Analysis-Calculated for C H O 8'.39%.'Found: C, 75.16%;H, 8.28%.

EXAMPLE VII A mixture comprised predominantly of 8 (and 9)-(3- butenyl)tricylclo[5.2.1.0 ]dec-3-ene was obtained as described in Example VI and isolated by fractional distillation (B.P. 56.5 C./0.35 mm. Hg63 C./0.45 mm.

' was thereafter removed by codistillation with 1500 grams of ethylbenzene. The residuewas then distilled through a 36-inch long column to give at first lower-boiling monoepoxides and then v482 grams of a colorless liquid'boil- I ing at a temperature of 125-127 C./0.6 mm. Hg (11 1.5068), which consisted of substantially pure 3,4-epoxy-8 (and 9)-(3,4-epoxybutyl)tricyclo [5.2.1.0 ]decane (indicated purity of 97.3 percent of hydrogen bromide-dioxane epoxide analysis).

Analysis.Calculated for C I-I 0 C, 76.32%; .H,

' 9.15%. Found: C, 76.18%; H, 8.90%.

EXAMPLE VIII A mixture of 400 grams of 3,4-epoxy-8 (and 9)-epoxyethyltricyclo[ 5.2.1.0 decane obtained as described in Example VI, 300 grams of ethanol solvent, and 20 grams of. wet Raney Nickel catalyst was hydrogenated in a3? liter stainless steel rocker bomb at a temperature of from 142C. to 150 C. over a period of twenty minutes, during whichtime the pressure within thebomb dropped from a high of 1500 p.s.i. to 575 p.s.i. The pressure was then brought back to 1500 p.s.i. and hydrogenation was continued at the same temperature foran additional three hours, during which time the pressure dropped from 1500 p.s.i. to 1400 p.s.i. Upon removal of the catalyst by filtration and the solvent by distillation, 398 grams of substantially pure 8 (and 9) (2 hydroxyethyl)tricyclo [5.2.1.0 ]decan-3 (and 4)-ol were obtained as a viscous residue (indicated purity 89.8 percent by phthalic anhydride-pyridine hydroxyl analysis).

Analysis-Calculated for C H O C. 73.43%; H, 10.27%. Found: C, 74.36%; H, 10.44%.

- EXAMPLE 1x I A mixture of 250 grams of 3,4-epoxy-8 (and 9) -(3,4- epoxybutyl)tricyclo[5.2.1.0? ]decane obtained as described in Example VII, 250 grams of ethanol, and 12.5 grams of wet Raney Nickel catalyst was hydrogenated in a 3-liter stainless steel rocker bomb at a temperature of from 145 C. to 154 C. over a period of three hours and twenty minutes, during which time the pressure within the bomb dropped from 'a high of 1500 p.s.i. to 900 p.s.i. Upon'removal of the catalyst by filtration and the solventby distillation, 248 gramsof substantially pure 8 (and 9) -(4-hydroxybutyl)tricyclo[5.2.1.0 ]decan-3 (and 4)-ol were obtained as a viscous residue (indicated purity 92.8 percent by phthalic anhydride pyridine hydroxyl analysis). i

We claim:

1. An isomeric mixture of diepoxides selected from the group consisting of diepoxides of the formula:

(cHzcHzmcl-l Cl-iz v 25 26 wherein n is an integer of from 1 to 16 and y is an integer References Cited from 0 UNITED STATES PATENTS 2. An isomeric mixture as in claim 1 wherein y is 0. 3. An isomeric mixture as in claim 2 wherein the di- 3,066,151 11/1962 Thorn et 26O 348 epoxides are 3,4-epoxy-8-epoxyethyltricyclo[5.2.1.0 3,247,137 4/1966 McGarY et decane and 3,4-epoxy 9 epoxyethyltricyclo[5.2.1.0 5

decane NORMA S. MILESTONE, Primary Examiner 4An isomeric mixture as in claim 2 wherein the di- U S Cl XR epoxides are 3,4 epoxy 8 (3,4-epoxybutyl)tricyclo [5.2.l.0. ]decane and 3,4-ep0xy-9-(3,4-epoxybuty1)tri- 260-2, 30.4, 448, 456, 617, 666 cyclo[5.2.l.0 ]decane. 10 

